Greases containing tetrahalophthalyl compounds and organophilic siliceous materials as thickeners



Patented July 3, 1962 ice This invention relates to improved lubricating compositions and more particularly to lubricants suitable for high temperature lubrication comprising a lubricating oil thickened primarily With certain high melting tetrahalophthalyl compounds.

The trend in design of modern aircraft has accentuated the need for greases which Will lubricate anti-friction bearings operating at high rotational speeds and high temperatures. While considerable progress has been tade in recent years in producing improved aircraft greases some dilliculty has been encountered in producing a grease which will effectively lubricate bearings operating at high rotational speeds and high temperatures for prolonged periods of time. Conventional aircraft greases currently available have failed to meet the stringent requirements on such a lubricant.

We have discovered htat a lubricating composition having improved lubricating characteristics for an extended period of time when used to lubricate bearings operating at an elevated temperature under high rotational speeds can be obtained by incorporating into a lubrieating oil in oil thickening proportions a tetrahalophthalyl compound selected from the group consisting of metal salts of tetrahalophthalic acid, monoesters of a tetrahalophthalic acid, metal salts of monesters of a tetrahalophthalic acid, monoand cliamides of a tetrahalophthalic acid and metal salts of monoamides of a tetrahalophthalic acid. Thus, the improved lubricating composition of our invention comprises a dispersion in a lubricating oil of a sufiicent amount to thicken the lubricating oil to a grease consistency of a tetrahalophthalyl compound of the type designated above. In some instances a secondary oil thickening agent comprising an organophilic siliceous material is also employed.

The amount of the oil thickening agent which We use whether simply the tetrahalophthalyl compotmd or a mixture of the tetrahalophthalyl compound and an organophilic siliceous material is an amount sufficient to thicken the lubricating oil to a grease having the desired consistency. In general, this amount comprises about 10 to about 60 percent by weight of the total composition. Vlhen a mixture of the tetrahalophthalyl compound and an organophilic siliceous material is used, the Weight ratio of the tetrahalophthalyl compound to the organophilic siliceous material will vary depending upon the characteristics desired in the ultimate composition. In general, however, the ratio of the tetrahalophthalyl compound to the organophilic siliceous material is between about 1:1 and about 50: 1.

etals forming the metal salts of the tetrahalophthalic acid and derivatives thereof useful as thickem'ng agents according to this invention include sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc. Of these metals, the alkali metals and alkaline earth metals form a preferred group. The alkali metal salts of a tetrahalophthalic acid are especially preferred thickening agents.

Specific examples of some of the metal salts of the tetrahalophthalic acids are:

Disodium tetrachlorophthalate Disodium tetrabromophthalate Disodium tetraiodophthalate Dipotassium tetrachlorophthalate Dilithium tetrabromophthalate Calcium tetraiodophthalate Barium tetrachlorophthalate Strontium tetrabromophthalate Aluminum tetraiodophthalate The monoesters of the tetrahalophthalic acids and the metal salts of the monoester of the tetrahalophthalic acids are represented by the formula:

Y C 0 OR H halophthalic acids and the metal salts of the monoesters of the tetrahalophthalic acids are: Mono-methyl tetrabromophthalate Mono-n-butyl tetraiodophthalate Mono-tertiary-butyl tetrachlorophthalate Mono-cyclohexyl tetrabromophthalate Mono-isooctyl tetraiodophthalate Mono-decyl tetrachlorophthalate Mono-dodecyl tetrabromophthalate Mono-tetradecyl tetraiodophthalate Mono-hexadecyl tetrachlorophthalate Mono-octadecyl tetrabromophthalate Mono-eicosyl tetraiodophthalate Mono-docosyl tetrachlorophthalate Mono-phenyl tetrabromophthalate Mono-naphthyl tetra-iodophthalate Sodium methyl tetrachlorophthalate Potassium n-butyl tetrabrornophthalate Lithium tertiary-butyl tetraiodophthalate Calcium cyclohexyl tetrachlorophthalate Barium isooctyl tetrabrornophthalate Strontium decyl tetraiodophthalate Sodium dodecyl tetrachlorophthalate Potassium tetradecyl tetrabromophthalate Lithium hexadecyl tetraiodophthalate Calcium octadecyl tetrachlorophthalate Barium eicosyl tetrabromophthalate Strontium docosyl tetraiodophthalate Sodium phenyl tetrachlorophthalate Sodium naphthyl tetrabromophthalate The monoand di-tetrahalophthalamates and the metal salts of the mono-tetrahalophthalamates are represented by the formula:

Y OOA and R are selected from the group consisting of H and aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms.

sesame Examples of R and R as aliphatic, alicyclic and aromatic hydrocarbon radicals include methyl, ethyl, propyl, n-butyl, tertiary butyl, pentyl, cyclopentyl, hexyl, 2,3-dimethylbutyl, cyclohexyl heptyl, 2-ethylhexyl, isooctyl, n-octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, phenyl, naphthyl, and the like.

Specific examples of some of the tetrahalophthalamates are:

N-methyl tetrachlorophthalamate N,N-dimethyl tetrabromophthalamate N-butyl tetraidophthalamate N,N-ditertiary-buty l tetrachlorophthalamate N-cyclohexyl tetrabromophthalamate N,N-dicyclohexyl tetraiodophthalamate N-isooctyl tetrachlorophthalamate N,N-diisooctyl tetrabromophthalamate N-octadecyl tetraiodophthalamate N-eicosyl tetrachlorophthalamate N-docosyl tetrabromophthalamate N-phenyl tetraiodophthalamate N,N-dipl1enyl tetrachlorophthalamate N-naphthyl tetrabromophthalamate Sodium N-methyl tetraiodophthalamate Potassium N,N-dimethyl tetrachlorophthalamate Lithium N-butyl tetrabromophthalamate Calcium N,N-ditertiary-butyl tetraiodophthalamate Barium N-cyclohexyl tetrachlorophthalamate Strontium N,N-dicyclohexyl tetrabromophthalamate Sodium N-isooctyl tetraiodophthalamate Potassium N,N-diisooctyl tetrachlorophthalamate Lithium N-octadecyl tetrabromophthalamate Calcium N-eicosyl tetraiodophthalamate Barium N-docosyl tetrachlorophthalamate Strontium N-pheny'l tetrabromophthalamate Sodium N,N-diphenyl tetraiodophthalamate Potassium N-naphthyl tetrachlorophthalarnate Methyl N-methyl tetrabromophthalamate Methyl N-butyl tetraiodophthalamate Methyl N,N-ditertiary-butyl tetrachlorophthalamate Methyl N-cyclohexyl tetrabromophthalamate Methyl N-isooctyl tetraiodophthalamate Methyl N-octadecyl tetrachlorophthalamate Methyl N-phenyl tetrabromophthalamate Methyl N-naphthyl tetraiodophthalamate Ethyl N-dodoecyl tetrachlorophthalamate Propyl N -hexadecyl tetrabromophthalamate Butyl N-octadecyl tetraiodophthalamate Pentyl N-isooctyl tetrachlorophthalamate Hexyl N-isooctyl tetrabromophthalamate Heptyl N-isooctyl tetraiodophthalamate Octyl N,N-diisooctyl tetrachlorophthalamate Dodecyl N-butyl tetraiodophthalamate Octadecyl N-butyl tetrachlorophthalamate Eicosyl N-butyl tetrabromophthalamate Decyl N-tetradecyl tetrabromophthalamate The tetrahalophthalyl compounds can be prepared according to known chemical procedures. Neither the compounds per se nor their preparation constitutes any portion of the invention. The metal salts, the amides and the esters can be prepared according to known salt-forming, amidation and esterification procedures, respectively. The following illustrative examples will serve to demonstrate the preparation of some of the specific tetrahalophthalyl compounds. The utility of these tetrahalophthalyl compounds in forming lubricating compositions of the invention is illustrated by the data presented in Table I.

EXAMPLE 1 (Disodium Tetrachlorophthalate) One hundred grams (0.386 mole) of tetrachlorophthalic anhydride was dissolved in 400 m1. of water containing the stoichiometric amount (30.9 gm.) of sodium hydroxide. Concentration of the solution yielded the disodium tetrachlorophthalate which was washed with a small i amount of water and then dried in an oven at C. for four hours. The product comprising disodium tetra chlorophthalate melted above 400 C. (752 F.).

EXAMPLE 2 (Disodium Tetrabramophthalate) Tetrabromophthalic anhydride (179.8 gm., 0.39 mole) was dissolved in 700 ml. of water containing the stoichiometric amount (31.2 gm., 0.78 mole) of sodium hydroxide. Concentration of the solution yielded the disodium tetrabromophthalate which was washed with a small amount of water and then dried in an oven at 100 C. The product comprising disodium tetrabromophthalate melted above 400 C. (752 F.).

The organophilic siliceous materials which We can employ as secondary thickening agents in the lubricating composition of this invention are exemplified by bentoniteorganic base compounds known commercially as Bentones and finely divided organo-siliceous solids such as the esterified siliceous solids known commercially as Estersils. The amount of the organophilic siliceous material employed may vary over wide limits depending upon the particular compound employed, the particular oil with which the siliceous compound is blended and the properties desired in the ultimate composition. While the organophilic siliceous material, when used, may comprise as much as 20 percent by weight of the total composition, we prefer to use smaller amounts, that is, in order of about 1 to about 10 percent by weight. It should be understood, however, that depending upon the consistency of the composition desired and upon the tetrahalophthalyl compound content of the composition less than 1 percent or more than 10 percent of the organophilic siliceous material can be employed.

Typical bentonite-organic base compounds which can be employed in accordance with the invention are compounds composed of a montmorillonite mineral in which at least a part of the cation content of the mineral has been replaced by an organic base. Clays that swell at least to some extent on being contacted with water and contain as a primary constituent a mineral of the group known as montmorillonites are generally referred to as bentonites. Such clays, which contain exchangeable alkali metal atoms either naturally or after treatment, constitute the raw materials employed in making the bentonite-organic base compounds used in the compositions of this invention. So far as known, all naturally occurring montmorillonites contain some magnesium and certain of them, as exemplified by Hector clay, contain such a high percentage of magnesium that they largely have magnesium in place of the aluminum content characteristic of the more typical montmorillonites.

The bentonite-organic base compounds are preferably prepared as described in US. Patent No. 2,033,856, issued March 10, 1936, by bringing together the bentonite and the organic base in the presence of aqueous mineral acid to effect base exchange. The organic bases should preferably be titratable with mineral acids. Among these reactive bases are many alkaloids, and cyclic, aliphatic, and heterocyclic amines. The bentonite-organic base compounds used in preparing the lubricating compositions of this invention are preferably those prepared by bringing together a bentonite clay and such organic bases as aliphatic amines, their salts, and quaternary ammonium salts. Examples of such amines and salts are: decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, hexadecyl ammonium acetate, octadecyl ammo nium acetate, dimethyldioctyl ammonium acetate, dimethyldidodecyl ammonium acetate, dimethyldodecylhexadecyl ammonium acetate, dimethyldicetyl ammonium ace tate, dimethylhexadecyloctadecyl ammonium acetate, dimethyldioctadecyl ammonium acetate, and the corresponding chlorides and quaternary ammonium chlorides. The organic bases employed should be such as to impart substantial organophilic properties to the resulting compounds The preferred bentonite compounds are prepared from quaternary ammonium compounds in which the N- substituents are aliphatic groups containing at least one alkyl group with a total of at least to 12 carbon atoms. When aliphatic amines are used they preferably contain at least one alkyl group containing at least 10 to 12 carbon atoms.

While the long chain aliphatic amine bentonite compounds are readily dispersible in practically all oil bases, dispersion of the short or single chain aliphatic amine bentonite compounds, in the oil, particularly mineral oils and synthetic oils other than ester lubricants, can be facilitated by the use of one or more solvating agents. Suitable solvating agents are polar organic compounds such as organic acids, esters, alcohols, ethers, ketones, and aldehydes, especially low molecular weight compounds of these classes. Examples of suitable solvating agents are: ethyl acetate, acetic acid, acetone, methyl alcohol, ethyl alcohol, benzoyl chloride, butyl stearate, cocoanut oil, cyclohexanone, ethylene dichloride, ethyl ether, furfural, isoamyl acetate, methyl ethyl ketone, and nitrobenzene. In cases where the use of a solvating agent is desirable for effecting more rapid and more complete dispersion of the organic bentonite compound in the oil, ordinarily only a relatively small amount of such agent may be necessary. However, as much as about 50 percent by weight based on the amount of the bentonite compound can be used.

Typical estersils which can be employed in accordance with the invention are described in U.S. Patent No. 2,657,149, issued October 27, 1953, to R. K. Iler. The estersils are organophilic solids made by chemically reacting primary or secondary alcohols with certain siliceous solids. In brief, the estersils are powders or pulverulent materials the internal structure or substrate of which have an average specific surface area of from 1 to 900 square meters per gram. The substrate has a surface of silica which is coated with OR' groups, the coating of OR' groups being chemically bound to the silica. R is a hydrocarbon radical of a primary or secondary alcohol containing from 2 to 18 carbon atoms. The carbon atom atached to the oxygen is also attached to hydrogen.

The estersil substrates are solid inorganic siliceous materials which contain substantially no chemically bound organic groups prior to esterification. The substrates are in a super colloidal state of subdivision, indicating that whatever discrete particles are present are larger than colloidal size. In general, the super colloidal substrates have at least one dimension of at least 150 millimicrons. The supercolloidal particles may be aggregates of ultimate units which are colloidal in size.

When we employ an estersil it is advantageously one in which the ultimate units have an average diameter of 8 to 10 millirnicrons. The substrates advantageously have specific surface areas of at least 25 square meters per gram and preferably at least 200 square meters per gram.

The estersils made from most alcohols become organophilic when they contain more than about 80 ester groups per 100 square millimicrons of surface of internal structure. They become more organophilic as the ester groups increase. Thus, the products which contain 100 ester groups per 100 square millimicrons of substrate surface are more organophilic than those that contain only 80 ester groups. When the estersils contain at least 200 ester groups per 100 square millimicrons of substrate surface, the estersils not only are organophilic but also are hydrophobic. Thus, the more highly esterified products are particularly desirable where the lubricant made therefrom comes in contact with water. When C to C alcohols are used in preparing the estersils, the estersils may contain from 300 to 400 ester groups per 100 square millimicrons of substrate surface. Thus, a preferred group of estersils are those prepared from the C to C alcohols. The estersils, as noted above, are powders or pulverulent we mean an oil of non-mineral origin.

materials. The estersil .powders are exceedingly fine, light and flufly. The bulk density of preferred estersils is in the order of 0.15 to 0.20 gram per cubic centimeter at 3 pounds per square inch and in the order of about 0.30 gram per cubic centimeter at 78 pounds per square inch. The estersils are available commercially and thus the estersils per se and their preparation constitute no part of this invention.

The lubricating oil in which the tetrahalophthalyl compound and the secondary thickening agent, when used, are incorporated is preferably a lubricant of the type best suited for the particular use for which the ultimate composition is designed. Since many of the properties possessed by the lubricating oil are imparted to the ultimate lubricating composition, we advantageously employ an oil which is thermally stable at the contemplated lubricating temperature. Some mineral oils, especially hydrotreated mineral oils, are sufiiciently stable to provide a lubricating base for preparing lubricants to be used under moderately elevated temperatures. Where temperatures in the order of 400 F. and above are to be encountered, synthetic oils form a preferred class of lubricating bases because of their high thermal stability. By the term synthetic oil The synthetic oil can be an organic ester which has a majority of the properties of a hydrocarbon oil of lubricating grade such as di-Z-ethylhexyl sebacate, dioctyl phthalate and dioctyl azelate. Instead of an organic ester, we can use polymerized olefins, copolymers of alkylene glycols and alkylene oxides, polyorgano siloxanes and the like.

The liquid polyorgano siloxanes because of their exceedingly high thermal stability form a preferred group of synthetic oils to which the tetrahalophthalyl compound and organophilic siliceous materials are added. These polyorgano siloxanes are known commercially as silicones and are made up of silicon and oxygen atoms wherein the silicon atoms may be substituted with alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals. Exemplary of such compounds are the dimethyl silicone polymers, diethyl silicone polymers, ethyl-phenyl silicone polymers and methylphenyl silicone polymers.

If desired, a blend of oils of suitable viscosity may be employed as the lubricating oil base instead of a single oil by means of which any desired viscosity may be secured. Therefore, depending upon the particular use for which the ultimate composition is designed, the lubricating oil base may be a mineral oil, a synthetic oil, or a mixture of mineral and/or synthetic oils. The lubricating oil content of the compositions prepared according to this invention comprises about 40 to about percent by weight of the total composition.

In compounding the compositions of the present invention, various mixing and blending procedures may be used. In a preferred embodiment of the invention, the lubricating oil, the tetrahalophthalyl compound and the secondary thickener, if used, together with a solvating agent and conventional lubricant additives, if desired, are mixed together at room temperature for a period of 10 to 30- minutes to form a slurry. During this initial mixing period some thickening is evidenced. Some lumps may be formed. The slurry thus formed is then subjected to a conventional milling operation in a ball mill, a colloid mill, homogenizer or similar device used in compounding greases to give the desired degree of dispersion. In the illustrative compositions of this invention, the slurry was passed twice, by means of a pump, through a Premier Colloid Mill set at a stator-rotor clearance of 0.002 inch. Maximum thickening occurred on the second pass through the mill.

The lubricating composition of this invention can contain conventional lubricant additives. if desired. to improve other specific properties of the lubricant without departing from the scope of the invention. Thus, the lubricating composition can contain a filler, a corrosion and rust inhibitor, an extreme pressure agent, an anti-oxidant, a metal deactivator, a dye, and the like. Whether or not such additives are employed and the amounts thereof depend to a large extent upon the severity of the conditions to which the composition is subjected and upon the stability of the lubricating oil base in the first instance. Since the polyorganosiloxanes, for example, are in general more stable than mineral oils, they require the addition of very little, if any, oxidation inhibitor. When such conventional additives are used they are generally added in amounts between about 0.01 and percent by weight based on the weight of the total composition.

In order to illustrate the lubricating characteristics at an elevated temperature and high rotational speeds, grease compositions of the invention were subjected to the test procedure outlined by the Coordinating Research Council Tentative Draft (July 1954), Research Technique for the Determination of Performance Characteristics of Lubricating Grease in Antifriction Bearings at Elevated Temperatures, CRC Designation L35. According to this procedure, 3 grams of the grease to be tested are placed in a bearing assembly containing an eight-ball SAE No. 204 ball hearing. The bearing assembly which is mounted on a horizontal spindle is subjected to a radial load of 5 pounds. The portion of the spindle upon which the test bearing assembly is located is encased in a thermostatically controlled oven. By this means the temperature of .the bearing can be maintained at a desired elevated temperature which in the tests reported hereinafter was 400 F. The spindle is driven by a constant belt-tension motor drive assembly, capable of giving spindle speeds up to 10,000 revolutions per minute. The spindle is operated on a cycling schedule consisting of a series of periods, each period consisting of 20 hours running time and 4 hours shutdown time. The test continues until the lubricant fails. vThe lubricant is considered to have failed when any one of the following conditions occurs, (1) spindle input power increases to a value approximately 300 percent above the steady state condition at the test temperature; (2) an increase in temperature at the test hearing of 20 F. over the test temperature during any portion of a cycle; or (3) the test bearing locks or the drive belt slips at the start or during the test cycle.

The oil used in preparing the lubricating compositions summarized in Table I was a synthetic oil known commercially as DC 550 Fluid marketed by Dow-Corning Corporation. This fluid is a methylphenylsiloxane polymer having as typical characteristics a viscosity at 100 F. of 300 to 400 SUS, a viscosity-temperature coefiicient 'of 0.75, a freezing point of 54 F., a flash point of 600 F. and a specific gravity 25 C./25 C. of 1.08.

The Estersil GT employed is marketed by E. I. du Pont de Nemours and Company and consists of an amorphous silica coated with approximately 340 butoxy groups per 100 square millimicrons of surface. The product is a white granular solid comprising 88 to 89 percent SiO having an ultimate particle size of 8 to 10 millimicrons. The surface area comprises about 285 to 335 square meters per gram. The product has a pH in a 5050 methanol-water mixture of 8.0 to 9.0 and a bulk density of 19 to 20 pounds per cubic foot.

TABLE I Composition, Percent By Weight Lubricating Oil: DC 550 Fluid Primary Thickener:

Disodium tetrachlorophthalate Disodium tetrabromophthalate Secondary Tbickener:

Dimethyldicetylammonium bentonite Estersil GT Inspection:

Penetration (ASTM D2l752T)- Unworked Worked Dropping Point, F. (ASTM 11566-42) Performance Life, Hrs-10,000 rpm. at 400 The long performance life of the compositions of the invention at a high rotational speed and a high temperature is self-evident from the above data.

Otherlubricating compositions Within the scope of the invention are illustrated in Table II. G.E. Silicon 81717 is marketed by General Electric Company and is a waterwhite to amber liquid polymer of the general formula It has a viscosity at F. of 3487 centistokes, at 0 F. of 390 centistokes, at F. of 71.3 centistokes, at 210 F. of 22 centistokes and at 700 F. of 1.9 centistokes.

TAB LE II Composition, percent By Weight Ratio of tetrahalophthalyl compound to secondary Lubricating Oil:

DC 550 Fluid G.E. Silicone 81717 Di-Z-ethylhexyl sebacatei;

Tetrahalophthalyl Compound:

Dipotassium tetrachlorophthalate Dilithium tetrabr0rnophtha1ate Calcium tetraiodophthalate Barium tetrachlorophthalate Aluminum tetraiodophthalate Mono-methyl tctrabrmngphthalate. Mono-isooctyl tetraiodophthalate Calcium cyclohexyl tetrachlorophthalate Barium eicosyl tetrabromophthalatc N-methyl tetrachlorophthalamate N,N-dimethyl tetrabromophthalamate Sodium N-methyl tctraiodophthalmnate.

Methyl N-n-octadecyl tetrach1orophtha1a mate Potassium N,N-diisooctyl tetrachlorophthalamate Secondary Thickener:

Dinlethyldicetylammonium bentonite I Dimethyldidodecylarmnonium bentonite Dimethyldioctylammonium bentonite Dimethyldioctadecylammonium bento Estersil GT thickener N While our invention has been described with reference to various specific examples and embodiments, itWill be understood that the invention is not limited to such examples and embodiments and may be variously practiced Within the scope of the claims hereinafter made.

Vie claim:

1. A lubricating composition comprising a dispersion in a lubricating oil of a sufiicient amount to thicken the lubricating oil to a grease consistency of a tetrahalophthalyl compound selected from the group consisting of metal salts of a tetrahalophthalic acid; tetrahalophthalates having the formula:

Y COOX Y COOR Where X is selected from the group consisting of hydrogen and a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc; Y is selected from the group consisting of chlorine, bromine and iodine; and R" is selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms; and tetrahalophthalamates having the formula:

Y OONRR where A is selected from the group consisting of OR, OM and NRR'; M is a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc; Y is selected from the group consisting of chlorine, bromine and iodine; and R and R are selected from the group consisting of hydrogen and aliphatic, alcyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms.

2. A lubricating composition comprising a dispersion in a lubricating oil of a sufficient amount to thicken the lubricating oil to a grease consistency of a mixture of a tetrahalophthalyl compound selected from the group consisting of metal salts of a tetrahalophthalic acid; tetrahalophthalates having the formula:

Y OOOR Where X is selected from the group consisting of hydrogen and a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc; Y is selected from the group consisting of chlorine, bromine and iodine; and R" is selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms;

and tetrahalophthalamates having the formula:

Y OONRR' Y COA 19 an organophilic siliceous oil thickening agent, the Weight ratio of the tetrahalophthalyl compound to the organophilic siliceous material in said mixture being about 1:1 to about 50:1.

3, The lubricating composition of claim 2 wherein the combined tetrahalophthalyl compound and organophilic siliceous material comprises about 10 to 60 percent by weight of the total composition.

4. The lubricating composition of claim 1 wherein the lubricating oil is a polyorgano siloxane.

5, The lubricating composition of claim 2 wherein the organophilic siliceous oil thickening agent i a bentoniteorganic base compound.

6. The lubricating composition of claim 2 wherein the organophilic siliceous oil thickening agent is an organophilic estersil comprising a supercolloidal substrate coated with -OR' groups, the substrate having a surface of silica and having a specific surface area of from 1 to 900 square meters per gram, the coating of OR groups being chemically bound to said silica and R being a hydrocarbon radical of from 2 to 18 carbon atoms, wherein the carbon attached to oxygen is also attached to hydrogen.

7. A lubricating composition comprising a dispersion in a liquid polyorgano siloxane of a suflicient amount to thicken the polyorgano siloxane to a grease consistency of a mixture of a tetrahalophthalyl compound selected from the group consisting of metal salts of tetrahalophthalic acid; tetrahalophthalates having the formula:

Y COOX OOOR Y COA Y Where A is selected from the group consisting of OR, OM and NRR'; M is a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc; Y is selected from the r group consisting of chlorine, bromine and iodine; and

R and R are selected from the group consisting of hydrogen and aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms; and an organophilic bentonite-organic base compound, the weight ratio of the tetrahalophthalyl compound to the organophilic bentonite-organic base compound in said mixture being about 1:1 to about 50:1.

8. A lubricating composition comprising a dispersion in a lubricating oil of a suflicient amount to thicken the lubricating oil to a grease consistency of a mixture of a tetrahalophthalylamate having the formula:

Y -o o NRR where A is selected from the group consisting of OR, OM and NRR; M is a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium,

strontium, aluminum and Zinc; Y is selected from the group consisting of chlorine, bromine and iodine; and R and R are selected from the group consisting of hydrogen and aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms and an organophilic siliceous oil thickening agent, the weight ratio of the tetrahalophthalamate to the organophilic siliceous material in said mixture being about 1:1 to about 50:1.

9. The lubricating composition of claim 8 wherein the tetrahalophthalamate is methyl N-n-octadecyltetrachlorophthalamate.

10. A lubricating composition comprising a dispersion in a lubricating oil of a suflicient amount to thicken the lubricating oil to a grease consistency of a mixture of a tetrahalophthalate having the formula:

Y COOX Y OOOR where X is selected from the group consisting of hydrogen and a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc; Y is selected from the group consisting of chlorine, bromine and iodine; and R is selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms and an organophilic siliceous oil thickening agent, the weight ratio of the tetrahalophthalate to the organophilic siliceous material in said mixture being about 1:1 to about 50: 1.

11. The lubricating composition of claim 10 wherein the tetrahalophthalate is mono-isooctyl tetraiodophthalate.

12. The lubricating composition of claim 10 wherein the tetrahalophthalate is mono-methyl tetrabromophthalate.

13. A lubricating composition comprising a dispersion in a lubricating oil of a sufiicient amount to thicken the lubricating oil to a grease consistency of a mixture of disodium tetrachlorophthalate and an organophilic siliceous oil thickening agent, the weight ratio of the disodium tetrachlorophthalate to the organophilic siliceous material in said mixture being about 1:1 to about 50: 1.

14. A lubricating composition comprising a dispersion in a lubricating oil of a sufficient amount to thicken the lubricating oil to a grease consistency of a mixture of disodium tetrabromophthalate and an organophilic siliceous oil thickening agent, the Weight ratio of the disodium tetrabromophthalate to the organophilic siliceous material in said mixture being about 1:1 to about 50.1.

15. A lubricating composition comprising a dispersion in a liquid polyorgano siloxane of a suflicient amount to thicken the polyorgano siloxane to a grease consistency of a mixture of disodium tetrachlorophthalate and dimethyldicetylammonium bentonite, the weight ratio of the disodium tetrachlorophthalate to the dimethyldicetylammonium bentonite in said mixture being about 1:1 to about 50: 1.

16. A lubricating composition comprising a dispersion in a liquid polyorgano siloxane of a suflicient amount to thicken the polyorgano siloxane to a grease consistency of a mixture of a tetrahalophthalyl compound selected i2 from the group consisting of metal salts of a tetrahalophthalic acid; tetrahalophthalates having the formula:

Y COOX OOOR Y C ONRR' Y OOA where A is selected from the group consisting of OR,

OM and NRR; M is a metal selected from the group consisting of sodium, potassium, lithium, calcium, barium, strontium, aluminum and zinc; Y is selected from the group consisting of chlorine, bromine and iodine; and R and R are selected from the group consisting of hydrogen and aliphatic, alicyclic and aromatic hydrocarbon radicals having from 1 to 22 carbon atoms; and an organophilic estersil, the Weight ratio of the tetrahalophthalyl compound to the organophilic estersil in said mixture being about 1:1 to about 50:1, said organophilic estersil comprising a supercolloidal substrate coated with OR groups, the substrate having a surface of silica and having a specific surface area of from 25 to 900 square meters per gram, the coating of OR groups being chemically bound to said silica and R being a hydrocarbon radical of from 3 to 6 carbon atoms, wherein the carbon atom attached to oxygen is also attached to hydrogen.

17. The lubricating composition of claim 16 wherein the tetrahalophthalyl compound is disodium tetrabromophthalate and the organophilic estersil is an amorphous silica coated with about 340 butoxy groups per square millimicrons of surface.

18. A lubricating composition comprising a dispersion in a liquid polyorgano siloxane of a suflicient amount to thicken the polyorgano siloxane to a grease consistency of a mixture of disodium tetrabromophthalate, dimethyldicetylammonium bentonite and an organophilic estersil comprising a supercolloidal substrate consisting of an amorphous silica coated with about 340 butoxy groups per 100 square millimicrons of surface, the weight ratio of the disodium tetrabromophthalate to the dimethyldicetylammonium bentonite and organophilic estersil in said mixture being about 1:1 to about 50: 1.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A LUBRICATING COMPOSITION COMPRISING A DISPERSION IN A LUBRICATING OIL OF A SUFFICIENT AMOUNT TO THICKEN THE LUBRICATING OIL TO A GREASE CONSISTENCY OF A TETRAHALOPHTHALYL COMPOUND SELECTED FROM THE GROUP CONSISTING OF METAL SALTS OF A TETRAHALOPHTALIC ACID; TETRAHALOPHTHALATES HAVING THE FORMULA: 